Mercury amalgam decomposition cell



Feb. 23, 1943. w. c. GNRDINR MERCURY AMALGAM DECOMPOSITIONA CELL Filed Aug. 19, 1959 -2 Sheets-Sheet4 l 34,4341? f f-L lNvENToR ATTORNEYS 70 7/ 72 73 74 7275 ya M J7 a .90' aro? 364 653.15

Feb-'23, 1943; W Q GARDllNER 2,311,744

MERCURY AMALGAM DECOMPOSITION CELL Filed Aug. V19, 1939 2\Sheets-Sheet 2 --i 1;@QQQLCQQQ5QQQQQ2QQQ;

W5 Je H53 64 as 67| s; @39m 96 t 99 'LJLIDJ u1u Lul m mmmmww mvENToR v /V///mm C 'afdzner BY @MN ATTORNEYS UNITED STATES PATENT OFFICE MERCURY AMALGAM nEcoMrosrrioN CELL William C. Gardiner, Niagara Falls, N. Y., assign- .or to The Mathieson Alkali Works, Inc., New e York, N. Y., a corporation of Virginia Application August 19, 1939, Serial No. 291,000

(Cl. ,2M-221) 2 Claims.

This invention is concerned with decomposition of amalgams of alkali metals, such as sodium and potassium. It provides improvements in mercury cells and the like to the end that such decomposition shall be facilitated and the alkali metal released more readily for reaction with water.

In the electrolysis of alkali metal salts, an alkali`metal amalgam is formed in an anode or amalgam-forming compartment, brought into contact with an aqueous electrolyte in a cathode `or decomposition compartment and there decomposed, the released alkali metal reacting with the water of' the electrolyte to form alkali metal hydroxide and hydrogen gas which is discharged at a cathode. Carbon and graphite are satisfactory cathode materials because they offer a relatively small resistance to the discharge of hydrogen and do not amalgamate and thus become coated with mercury, but they offer a high resistance to discharge of alkali metal. By coupling the carbon or graphite cathode electrically to the amalgam, -Which acts as anode in the decomposition compartment, the short-circuit developed facilitates the release of the alkali metal from the amalgam 'and permits the cell to operate with a higher current emciency than otherwise would be attained. Decomposition of the amalgam is facilitated further, and cell eiiiciencies' `consequently improved, if the cathode is electrically coupled to the amalgam by means of a metal member making a contact of low electrical resistance both with the carbon or graphite cathode and with the amalgam.

Asa result of my investigations, I have developed a novel cathode structure that employs this principle to facilitate amalgam decomposition which has several advantages. In the cathode structure of my invention, the carbon or graphite cathode elements are short-circuited by metal members disposed to make low resistance electrical connection between the cathode elements and the amalgam in the cell .and to support the cathode elements above the bottom of the decomposition compartment so as to reduce the mechanical resistance to flow of mercury through the compartments. The cathode structure of my invention is simple and inexpensive to construct and install and has a further advantage in that it is composed of units which are simple `and inexpensive to replace.

ithal, this cathode structure is considerably more emcient in bringing about amalgam decomposition than are conventional cathodes.

My invention contemplates, in apparatus in which an alkali metal from an anode of an amalgam of the alkali metal is reacted with a superposed body of aqueous electrolyte in contact with the anode to form hydrogen gas and hydroxide of the alkali metal in a compartment through which the amalgam moves, the combination which comprises a cathode Iformed of a plurality of substantially horizontal bars of graphite or carbon, heid side byside and spaced from each other in said body, and a plurality of metal supports which project into the anode and rest upon the bottom of the compartment, said metal supports being low in electrical contact resistance with the cathode elements, the carbon or graphite bars, and supporting it above and out of contact with the bottom of the compartment.

In my preferred form of cathode structure the metal supports serve both as supports and as spacers for the graphite or carbon bars and'are in the form of elongated substantially horizontally disposedv metal plates or strips resting on 'edge and parallel to each other on the bottom of the compartment and having a series of apertures in which the bars are fitted so as to provide low resistance electrical contact. This structure is with advantage disposed in the compartment with the metal plates substantially parallel to the path of amalgam movement, so as to furnish mimimum obstruction thereto, the

amalgam flow thus being across the several carviously-described, or the slots may be arranged substantially parallel to the direction of amalgam movement, but in either case the carbon or graphite elements of the grid are positioned in contact with the amalgam.

My invention will be more thoroughly understood in the light of the following detailed description taken in conjunction with the accompanying drawings of presently preferred types of cathodes of my invention and in which Fig. l is a fragmentary elevation, partly in section, taken through the decomposition compartment vpartmerlt |5A, fragmentarily shown.-

cathode of my invention having metallic contact i.,

pins or legs extending from the cathode grid through the amalgam to thebottompffthe come f,

partment;

Fig. 4 is an elevation, partiy'f in section, ftaler" through the apparatus of Fig.,l 3alongthelsecm tion line B-B;

Fig. 5 is a plan view of the preferred' form 'of cathode structure of my invention, thevdirectionof amalgam flow in the cell being parallel toV the member'sil and 99; and, f

.f l. 1 Fig. 6 is a fragmentary elevation, partly infsection, taken through`r the decomposition compart- :mentlof a mercury .cell jalong'theline ofamalgam ow, With'the cathodeA structure `of Fig..V zresting upon the bottom of Vthe compartment. l. j

Referring now to -Figsg land 2, it willv be observed that a conventional'.decompositionicompartment I cfa mercurycellhaving walls II,

IIA,` I2,l I2A and a substantiallyhorizontal.bot-

tom I3 of insulating materialis provided with` a conduitl I4 which enters the compartment atfone side adjacent the lbottom thereof and'` ,through which sodium amalgam. is introduced to @form` a layer I5 at'thebottom of the 4cell."` `',l'he sodium amalgam-for use in the decomposition `compartment is produced in the conventional mannerin an adjacent anode or` amalgam-forming com- The layer of sodium amalgam in the bottom of the decomposition compartmentiisoverlaidy by a body of aqueous electroiyteIS, such, for example, as an aqueous sodium hydroxide solution: Immersed within the electrolyte is a'serles of horizontally disposed elongated graphite,bars,11,1] 8,7` l I9, 20, 2|, 22, 23,`2425. The lower edges ofvthese `bars are` disposed uintcontact with the 'layer :of *amalgam* Vertical holes areydrilled in theV bottom of each of'the bars togreceive a seriesaof cylindrical iron pins-26, 21, 28,29, 3i),` 3|, 32, ,33, 34, 34A, 34B, which are fitted tightly into the holes, so as to make low resistance electrical contact with the graphite, and extend. downwardly through the amalgam layer, resting upon the bottom' of the decomposition compartment.- `The graphite bars are heidi in vparallel lspaced ,rela-l tionship by means of `avpairfoifiro'n tiegrods,

36, which extend horizontally throughmoles in the respective bars andv through small annular of the `tie rods are securedby threaded n uts.v

It'. will be observed thatthe pins serveas legs uponwhich the Vgraphite 'cathode .assembly rests, `there being at least twoplns .disposed `in opposite ends of each grid. .c f i, The balance of the structure of Figi-land of Fig; 2 is'thatof a conventionalA mercury cell,A In the amalgam-forming compartmentgyan `anode isdispose'd lin contact with 'an aqueous, solution cury that' acts' as cathodeintthe :compartment and picks up -the sodium formedby` decomposition of the= sodium Vchloride .to Vform.,the;` amalgam i which is' 1. clecomposedain 'fthe ,fcathode, compartment. In this 4decomposition sodium-isfreleased decomposition"compartment 4S` having walls 41,

, l 41A, 48, 48A, and a bottom 49 of insulating mafterial. A layer 50 of sodium amalgam formed,

. for, 1exampl e, g in an adjacent amalgam-forming compartment 5I, isintroduced into the bottom of 1'5 thedecompositioncompartment through a con- 'j 1f duitf52 andtlierecomes in contact with an overlying pool of 'adueous electrolyte 53, such as sodizum;` hydroxide solution. In this case, a cathode 541s formed of a plurality of elongated cylindri- "20 argraphite bars '55, 5s, s1, 5s, sa, en, si, sz, sa,

Gif 6,5,- ;dispo sed herizmltally;ami.4 spaced .slightly above the .layer-,of sodiuml amalgam.. The maior axesof theigraphitecylinders aredisposed trans- -Vversely f to, LtheE direction `of" l amalgam` flow, and

25 each cylinder is. Supportedeion.thefhottgm.of the decomposition compartmentby afpair; o f iron lor nickel pins or legs 66, 61, which are ttedtightly inw Yertiwl` holesffrlled 11,1 the Abttolilf 0f `with .,yllrider f 4The D s; rest` 1490.11. the; betteln lof 'the t ao decomposition www and "psslthoueh .t @tendinaheweiailyattrigg nglltathe axes ofthe graphite.. cylinders are pair 1ortie feds es, sa of ironyorgtaej like; y Triesjrtds bass through holesinthegraphite cylinders ,and also through holes ,'.Ilsihall annularironspace mmbers 10,11, 12x13, 141-; 6511.', 118..;193disne`d respectively.i between adJacp-cnt cylinders; N uts `are threaded on.thecendsQofffthefte `:frodsfffor `tightening the assempiy'sp that the graphite cylinders are held from eachother'in parallels'paced relationship.v f. j d The cathode structurersldescribedlhereinbefoe. and `especiany that iuusra'ted" m1 ms@ 'ai ,and` ,4. are ,simplev and `:efiicien "l, Howev,er, the structure ,llluStr-eed 1P; ne? .fi-ilsA @faullxeiciefnt `pier iadejsigagc i jl "trueaandioe JUgged, and fis therefore fpref ed; L Referring new, .to nes-5 and 'ein willsbe. ob 'wed that the Q-@milde St-IuillfeviolfriPfSf-*S Sries' bfiiefizl tallydisposed graphitve'jrodsor ,bai-'s4'` `80,190` 91,`,'i4 elusive- .i-The here eiidi'sbasedap'aralllteadh .other and spaced.l a ,Snflgl' @istante .natbtlt least E@ inch; #Qifisuradquat s'ba rrlh'ydragen disghersaliepe `heldin Siwh positienby a Pair. .0f `metal spacer members $8. 98. fwhichalso serve ,to support the` rods a shortgdisftancel above the bottomjfl., .4. a conventicnal: deenipastin Compartment l0. mereiiry vell-av `,'Iheup.- lports are prpvided with, @serie QI.KiirclllrA aperitures ubstentilliwthe l semeAmdiawter. asf the vroda.;which.,argiittelfiiahtly therento sol ast0 `afford.ieaudielecticelv nntaqizai l Sodumamalgamftolhevdecomposedfinthedecomposition,Compartmeltis ,fQrmedin `:irradiacent amalgamfornniing` compartment In I fragmentarily mwa-.ang lsf,passed:through-.fa lte -0,r;hydrai111 ;f,seal 10% to fo s layer-5in: inthe -betwmpitlieleomnartmeatrhefemphitefrds are. upncrted'. abovethe :bottom- Aof; th, .compartmenta distancesliehtly less than the, 'thickness pf the amaigam-layerisofthat the rods ineke .cn-

tactf therewith @ver abpt one .aquarien-Far their Surface. but damit. interfereseriouslylnihW of the mercury back and forth between the amalgam-forming compartment and the decomposition compartment. As illustrated in Fig. 6, the rods are disposed transversely to `the path of amalgam movement while the supporting members are substantially parallel to the path of movement. The movement; of the mercury against the rods aids in sweeping oi hydrogen from them, thereby facilitating amalgam decomposition.

The amalgam layer in the decomposition compartment is covered by a pool of aqueous electrolyte |04, such as sodium hydroxide solution, which also covers the cathode structure. A space for the reception of hydrogen discharged in the process is provided at the top of the compartment, which is closed by a cover |06 having a. hydrogen outlet conduit |01.

The graphite rods may, of course, be of other than circular section but the latter is a convenient form, because it enables the apertures to be formed in the supporting members by drilling in a simple and accurate manner. The size of the rods may be varied depending upon the size of the compartment in which they are disposed. I have found, however, that graphite rods having a minimum diameter of 0.50 inch and a maximum diameter of 0.54 inch are desirable. Such rods may be spaced apart about one-eighth inch and the space between the rods thus provided is adequate for hydrogen discharge. With rods of the size described, I have found that the supports may be spaced from each other at least 12 inches without placing excessive stress on the rods. The spacers may be made conveniently of cold rolled steel strips of No. 2 temper, 11g inch thick and 'V8 inch wide, with the holes for the reception of the rods spaced along the center line thereof. It is desirable to press t the graphite or carbon rods into the supporting members to insure adequate electrical contact.

In the event that the cathode must be removed for repair, it is easily lifted out of the compartment. Repair is also a simple matter in that broken rods may be driven out of the supporting members and a new rod driven or pressed in from the outside end of the structure.

Cathode assemblies, such as that illustrated in Figs. 3, 4, 5 and 6, in which the graphite bars or cylinders have their major axes transverse to the path of amalgam movement, are particularly desirable in that with such structures it is possible to maintain a very low ,concentration of alkali metal in the amalgam, thus increasing the current eilciency of the mercury cell in which the cathode is disposed. To illustrate, the cathode assembly similar tothat illustrated in Figs. 3 and 4 was disposed in a Castner type cell with the axes of the cylinders disposed substantially parallel to the path of mercury movement, and it was found that the amalgam attained a sodium concentration of 0.022%. The cathode assembly was then turned 90 in -the cell so that the major axes of the bars were at right angles to the path of mercury movement, and with all other conditions of operation remaining the same the concentration of sodium in the amalgam dropped to 0.018%, with consequent improvement in current efficiency. Y

It will be observed that the metal pins or legs or supports in the cathode assemblies illustrated herein keep the cathode elevated at a desirable height so that the amalgam may ow underneath and disposed at the optimum angle with respect to the direction of flow for good current eciency.

The supports are best so dimensioned that the amalgam layer is in contact with the carbon or graphiteelements when these elements are disposed transversely of the path of amalgam movement, as in Figs. 3,'4, 5 and 6. When the path of amalgam movement is substantially parallel to the major axes of the carbon or graphite bars the level of the amalgam also is with advantage maintained in contact with the bottom of the carbon or graphite bars, as in Figs. 1 and 2.

The following tests serve to illustrate the benets to be derived from the use of metallic contact members for establishing low resistance electrical contact between graphite cathodes and an anode of mercury amalgam in accordance with my invention.

Test No.1

A cube of graphite, the edges of which were all 1 cm. long, was placed on a layer of mercury amalgam containing approximately 0.1% sodium and both amalgam and cube were covered with an aqueous solution containing 30% by weight of sodium hydroxide. The graphite almost immediately became coated with a layer of hydrogen bubbles which did not become detached or released to any substantial degree and which seemed to insulate the graphite from the amal- Test No. 2

The cube of graphite resting on the amalgam layer was weighted down so that its lower edge was approximately 3 mms. under the amalgam surface. There was a slight increase in the hydrogen evolution under these circumstances, but hydrogen bubbles again rapidly blanketed the graphite and appearedto act as insulation, inhibiting hydrogen evolution and consequently inhibiting the rate at which sodium was released from the amalgam.

Test No. 3

In this test a hole having a diameter of 11e inch was` drilled into one face of the graphite cube. A clean iron pin was driven into the hole so as to form a tight lit and was then cut off so that approximately 11g inch of the pin protruded. The cube was then placed on the sodium amalgam under the sodium hydroxide solution with the iron pin in contact with the amalgam. Immediately there was a vigorous and continuing evolution of hydrogen from the graphite.

Test No. 4

A graphite cube .was placed on a layer of sodium amalgam and both were immersed in a solution containing 30% by weight of sodium hydroxide. The potential developed between the graphite cube and the sodium amalgam under such circumstances was measured, and it was found that the drop between the graphite and the amalgam was 0.300 volt. A metal pin was then driven into a hole in the graphite cube and placed in contact with the amalgam. Under these circumstances, potential measurements showed a voltage drop of only 0.00038 volt between the graphite cube and the sodium amalgam.

In the light of the tests, it is clear that the metal supports of my invention aid greatly in reducing the contact resistance between the mercury and the graphite, and bring about a remarkable increase in the rates at which hydrogen is evolved from a graphite or carbon cathode and at which the alkali metal is released from the amalgam.

I claim:

1. In apparatus in which an alkali metal from an anode of an amalgam of the alkali metal is reacted with a superposed body of aqueous electrolyte in contact with the anode to form hydrogen gas and hydroxide of the alkali metal in a compartment through which the amalgam moves, the combination which comprises an approximately level grid composed of a. plurality of cathode bars of a material selected from the group consisting of carbon and graphite and a plurality of metal spacer strips each provided with holes into which the bars. project in good electrical contact with the strips, the bars being held side by side but spaced from each other by the strips and supported by the strips in the body in contact with the amalgam but out of contact with the bottom o! the compartment, with the strips resting upon said bottom in contact with the amalgam.

2. In apparatus in which an alkali metal from an anode of an amalgam of the alkali metal is reacted with a superimposed body of aqueous electrolyte in contact with the anode to form hydrogen gas and hydroxide of the alkali metal in a compartment through which the amalgam moves, the combination which comprises an approximately level grid composed of a plurality of cathode bars of a material selected from the group consisting of carbon and graphite and a plurality of metal spacer strips each provided with holes into which the bars project in good electrical contact with the strips, the bars being held side by side but spaced from each other by the strips and supported bythe strips in the body in contact with the amalgam but out of contact with the bottom of the compartment with the strips resting upon the bottom in contact with the amalgam and extending in the direction of amalgam movement and transverse to the major axes of the bars.

WIILIAM C. GARDINER.. 

